聚邻甲苯胺(POT)、聚2,5二甲氧苯胺(PDMAn)和聚间氯代苯胺(PClAn)由化学法合成而得,用它们的二甲基甲酰胺溶液在铂上成膜以制得聚合物修饰电极.循环伏安实验表明:在1mol/LH2SO4中,POT的氧化还原分两步进行,呈现两对氧化还原峰,PDMAn只在较负的电位区呈现两对氧化还原峰,而PClAn不呈氧化还原活性.不同电位下的交流阻抗特征与循环伏安图相对应.三种聚合物膜电极在0.5mol/LK3[Fe(CN)6]溶液中的伏安图也证明铁氰离子的还原速度依POT>PDMAn>PClAn的顺序而下降.环取代基的影响用电子效应和几何效应进行解释.可溶性聚苯胺便于制作大面积器件,环取代基对调节聚苯胺的电化学性能具有重要作用,值得进一步研究.
1MacDiarmidAG.Polyanilineandpolypyrrole:whereareweaheaded?Synth.Met.,1997,84:27~342KitaniA,SstoguchiK,TangH,ItoS,SasakiK.Solublepolyanilinespreparedbyoxidativepolymerizationofanline.Synth.Met.,1995,69:131~1323IchinoheD,AraiT,KiseH.Synthesisofsolublepolyanilineinreversedmicelarsystems.Synth.Met.,1997,84:75~764GeniesEMetal.Polyaniline:ahistoricalsurvey.Synth.Met.,1990,36:139~182.5FujitaI,IshigushiM,ShiotaH,DanjoT,KosaiK.SpectroscopicstudyofpolytoluidinesintheUVvisibleandIRregions.J.Appl.PolymerSci.,1992,44:987~992.6AndradeEM,MolinaFV,FloritML,PosadasD.IRresponseofpoly(otoluidine):spectralmodificationsuponredoxstatechange.J.Electroanal.Chem.,1996,419:15~21.7VorotyntsevMA,DaikhinLI,LeviMD.Modelingtheimpedancepropertiesofelectrodescoatedwithelectroactivepolymerfilms.J.Electroanal.Chem.,1994,364:37~49.8SatoM,YamanakaS,NakayaJ,HyodoK.Propertiesofcyanidefunctionalizedpolyanilinepreparedbyoxidativeelectrochemicalpolymerizationofoaminobenzonitrile.J.ChemSoc.Chem.Commun.,1991,650~6519RangerM,LeclercM.Synthesisandcharacterizationofpolyanilineswithelectronwithdrawingsubstituents.Synth.Met.,1997,8485~86.